CN110036013A - Heterocyclic compound and the organic light emitting apparatus for using this heterocyclic compound - Google Patents

Heterocyclic compound and the organic light emitting apparatus for using this heterocyclic compound Download PDF

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CN110036013A
CN110036013A CN201780074623.5A CN201780074623A CN110036013A CN 110036013 A CN110036013 A CN 110036013A CN 201780074623 A CN201780074623 A CN 201780074623A CN 110036013 A CN110036013 A CN 110036013A
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heterocyclic compound
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CN110036013B (en
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罗炫柱
许柔珍
郑元场
崔珍硕
崔大赫
李柱东
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HISUNG MATERIAL CO Ltd
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    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
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Abstract

Present application is about a kind of heterocyclic compound indicated by chemical formula 1 and a kind of organic light emitting apparatus comprising this heterocyclic compound.

Description

Heterocyclic compound and the organic light emitting apparatus for using this heterocyclic compound
Technical field
Present application advocates on November 30th, 2016 in Wise property office, South Korea (Korean Intellectual Property Office) application South Korea patent application case the 10-2016-0162219th and on October 19th, 2017 in South Korea Wise property office application South Korea patent application case the 10-2017-0135667th priority and rights, entire contents with The mode of reference is incorporated herein.
Present application is related to a kind of heterocyclic compound and the organic light emitting apparatus using this heterocyclic compound.
Background technique
El light emitting device be a kind of automatic luminous display device, and have advantage, the advantage be with wide viewing angle with And very fast response speed and there is splendid contrast.
Organic light emitting apparatus has the structure for disposing organic film between two electrodes.There is this when applying a voltage to When the organic light emitting apparatus of class formation, combines and match in organic film from the electronics of two electrode injections and hole, and It shines when told electronics and the hole are buried in oblivion.Single-layer or multi-layer organic film can optionally be formed.
Optionally, there can be light-emitting function for the material of organic film.For example, it can be used alone and be capable of forming hair Material of the compound of photosphere as organic film itself, or also can be used can be used as main body-doping species (host- Dopant-based) the compound of the main body of luminescent layer or dopant.In addition, also can be used can play hole injection, hole turn Shifting, electronic blocking, hole barrier, electronics transfer, electron injection and similar effect material of the compound as organic film.
The development of organic film material constantly requires to promote efficiency, service life or the efficiency of organic light emitting apparatus.
Summary of the invention
Technical problem
Present application is about providing a kind of novel heterocyclic compounds and filled using the organic light emission of this heterocyclic compound It sets.
Technical solution
One embodiment of present application provides a kind of heterocyclic compound indicated by following formula 1:
[chemical formula 1]
In chemical formula 1,
At least one of R1 to R5 is by-(L1) p- (Z1) q expression, and remaining is hydrogen, the C for being substituted or being unsubstituted6 To C60Aryl or C2To C60Heteroaryl,
L1 is direct key；The C for being substituted or being unsubstituted6To C60Arlydene；Or C2To C60Inferior heteroaryl,
Z1 is selected in the group as composed by following persons: halogen；-CN；The C for being substituted or being unsubstituted1To C60Alkyl；Through The C for replacing or being unsubstituted6To C60Aryl；The C for being substituted or being unsubstituted2To C60Heteroaryl；-SiRR'R"；- P (=O) RR'；And it is unsubstituted or through C1To C20Alkyl, C6To C60Aryl or C2To C60The amido that heteroaryl replaces,
The integer that p is 0 to 4,
The integer that q is 1 to 4,
R6 to R13 is same or different to each other, and selects in the group being made of each independently following persons: hydrogen；Deuterium；Halogen；- CN；The C for being substituted or being unsubstituted1To C60Alkyl；The C for being substituted or being unsubstituted2To C60Alkenyl；It is substituted or is unsubstituted C2To C60Alkynyl；The C for being substituted or being unsubstituted1To C60Alkoxy；The C for being substituted or being unsubstituted3To C60Naphthenic base；Through The C for replacing or being unsubstituted2To C60Heterocyclylalkyl；The C for being substituted or being unsubstituted6To C60Aryl；It is substituted or is unsubstituted C2To C60Heteroaryl；-SiRR'R"；- P (=O) RR'；And it is unsubstituted or through C1To C20Alkyl, C6To C60Aryl or C2 To C60The amido that heteroaryl replaces, or be bonded adjacent to each other, each other to form the aliphatic ring for being substituted or being unsubstituted or aromatics Two of hydrocarbon ring or it is greater than two groups,
M and n is each independently 0 to 5 integer, and
R, R' and R " is same or different to each other, and is each independently hydrogen；Deuterium；-CN；The C for being substituted or being unsubstituted1 To C60Alkyl；The C for being substituted or being unsubstituted3To C60Naphthenic base；The C for being substituted or being unsubstituted6To C60Aryl；Or it is substituted Or the C being unsubstituted2To C60Heteroaryl.
Another embodiment of present application provides a kind of organic light emitting apparatus, and the organic light emitting apparatus includes anode, yin Pole and the organic material layer being set between anode and cathode, wherein one or more layers in organic material layer include jeterocyclic chemistry Close object.
Invention effect
Heterocyclic compound according to an embodiment of the invention can be used as the organic material layer material of organic light emitting apparatus. The heterocyclic compound can be used as in organic light emitting apparatus hole injection layer, hole transport layer, luminescent layer, electronics transfer layer, Electron injecting layer, charge generation layer or the material of fellow.Particularly, the heterocyclic compound indicated by chemical formula 1 is organic It can be used as the material of electronics transfer layer or charge generation layer in light emitting device.In addition, use is by chemistry in organic light emitting apparatus The heterocyclic compound that formula 1 indicates reduces the driving voltage of device, enhances light efficiency, and can pass through the thermal stability of the compound The life characteristic of enhancement device.
Detailed description of the invention
Fig. 1 to Fig. 4 is attached drawing, and each attached drawing schematically illustrates organic hair according to an embodiment of the invention The laminated construction of electro-optical device.
<symbol description>
100: substrate
200: anode
300: organic material layer
301: hole injection layer
302: hole transport layer
303: luminescent layer
304: hole blocking layer
305: electronics transfer layer
306: electron injecting layer
400: cathode
Specific embodiment
Hereinafter, it will be described in detail present application.
It is indicated according to the heterocyclic compound of one embodiment of present application by chemical formula 1.More precisely, by chemical formula 1 heterocyclic compound indicated can be used as the material of the organic material layer of organic light emitting apparatus, and the compound has this nucleoid The structure feature of core structure and substituent group.
In one embodiment of present application, when the p of chemical formula 1 is two or more, but two or be greater than two L1 that This is identical or different.In addition, two or greater than two Z1 can be same or different to each other when the q of chemical formula 1 is two or more.
In one embodiment of present application, at least one of R1 to R5 of chemical formula 1 is by-(L1) p- (Z1) q table Show, and remaining can be hydrogen.
In one embodiment of present application, R3 of the R1 of chemical formula 1 into R5 is indicated by-(L1) p- (Z1) q, and its Yu Kewei hydrogen.
In one embodiment of present application, R4 of the R1 of chemical formula 1 into R5 is indicated by-(L1) p- (Z1) q, and its Yu Kewei hydrogen.
Specifically, ought wherein chemical formula 1 R3 or R4 of the R1 into R5 position warp-(L1) p- (Z1) q substituent group When substituted compound is subsequently used as the material of electronics transfer layer of organic light emitting apparatus, intermolecular interaction be it is smooth with Conducive to intermolecular electron transfer.
The compound that wherein substituent group of position warp-(L1) p- (Z1) q of the R1 or R5 of chemical formula 1 replace and wherein chemistry The compound that the substituent group of position warp-(L1) p- (Z1) q of R3 or R4 of the R1 of formula 1 into R5 replace is compared with bigger point Sub- size, and therefore, due to reduced interaction of molecules, the amount of electron transfer reduces.
In one embodiment of present application, the L1 of chemical formula 1 can be direct key；The C for being substituted or being unsubstituted6Extremely C60Arlydene；Or C2To C60Inferior heteroaryl.
In another embodiment, the L1 of chemical formula 1 can be direct key；The C for being substituted or being unsubstituted6To C40Arlydene； Or C2To C40Inferior heteroaryl.
In another embodiment, the L1 of chemical formula 1 can be direct key；C6To C40Arlydene；Or C2To C40Inferior heteroaryl.
In another embodiment, the L1 of chemical formula 1 can be direct key；Phenylene；Join sub- diphenyl；Anthrylene；Naphthylene； Divalent imidazo [1,2-a] pyridyl group；Divalent pyridine base；Divalent pyrimidine radicals；Divalent triazine radical；Divalent quinazolyl；Or divalent Benzimidazolyl.
In one embodiment of present application, select: being substituted in the group that the Z1 of chemical formula 1 can be made of following persons or The C being unsubstituted1To C60Alkyl；The C for being substituted or being unsubstituted6To C60Aryl；The C for being substituted or being unsubstituted2To C60It is miscellaneous Aryl；P (=O) RR'；-CN；And it is unsubstituted or through C6To C60Aryl or C2To C60The amido that heteroaryl replaces.
In another embodiment, it is selected in the group that the Z1 of chemical formula 1 can be made of following persons: being substituted or be unsubstituted C1To C40Alkyl；The C for being substituted or being unsubstituted6To C40Aryl；The C for being substituted or being unsubstituted2To C40Heteroaryl；P (=O) RR'；-CN；And it is unsubstituted or through C6To C40Aryl or C2To C40The amido that heteroaryl replaces.
In another embodiment, it is selected in the group that the Z1 of chemical formula 1 can be made of following persons: C1To C40Alkyl；Without taking Generation or via P (=O) RR', C6To C40Aryl and C2To C40One or more substituent groups selected in the group of heteroaryl composition take The C in generation6To C40Aryl；It is unsubstituted or via C1To C40Alkyl, C6To C40Aryl and C2To C40In the group of heteroaryl composition The C that one or more substituent groups selected replace2To C40Heteroaryl；- P (=O) RR'；And-CN.
In another embodiment, it is selected in the group that the Z1 of chemical formula 1 can be made of following persons: C1To C40Alkyl；Without taking Generation or via P (=O) RR', C6To C40Aryl and C2To C40One or more and three selected in the group of heteroaryl composition Or the C replaced less than three substituent groups6To C40Aryl；It is unsubstituted or via C1To C40Alkyl, C6To C40Aryl and C2Extremely C40One or more and three that are selected in the group of heteroaryl composition or the C replaced less than three substituent groups2To C40Heteroaryl；-P (=O) RR'；And-CN.
In another embodiment, select: being unsubstituted in the group that the Z1 of chemical formula 1 can be made of following persons or via P (= O) the phenyl that one or more substituent groups selected in the group of RR', phenyl and carbazyl composition replace；Be unsubstituted or through P (= O) the naphthalene that RR' replaces；It is unsubstituted or via one or more substituent groups selected in the group of P (=O) RR' and naphthalene composition Substituted anthryl；Xenyl；Join sub- triphenyl；And phenanthryl.
In another embodiment, it is selected in the group that the Z1 of chemical formula 1 can be made of following persons: ethyl；P (=O) RR；With And-CN.
In another embodiment, the Z1 of chemical formula 1 can be to be unsubstituted or via C1To C40Alkyl, C6To C40Aryl and C2To C40The C that one or more substituent groups selected in the group of heteroaryl composition replace2To C40Heteroaryl, and heteroaryl may include making For at least one or more in heteroatomic N, O and S.
In another embodiment, it selects: being unsubstituted or via benzene in the group that the Z1 of chemical formula 1 can be made of following persons The pyridyl group that one or more substituent groups selected in the group of base, naphthalene and pyridyl group composition replace；It is unsubstituted or via benzene The pyrimidine radicals that one or more substituent groups selected in the group that base, xenyl, naphthalene and pyridyl group form replace；Be unsubstituted or The triazine radical that one or more substituent groups selected in group via phenyl, xenyl, naphthalene and pyridyl group composition replace；Without The quinazolyl for replacing or replacing via one or more substituent groups for selecting in the group of phenyl, xenyl and naphthalene composition；Quinoline Quinoline base；Carbazyl；The coffee quinoline base for being unsubstituted or replacing through phenyl；The imidazo [1,2-a] for being unsubstituted or replacing through phenyl Pyridyl group；The benzimidazolyl for being unsubstituted or replacing through ethyl；The benzothiazolyl for being unsubstituted or replacing through phenyl；Pyridine And [1,2-b] indazolyl；The oxadiazoles base for being unsubstituted or replacing through phenyl；The pyrazolo for being unsubstituted or replacing through phenyl [1,5-c] quinazolyl；And 1,5- naphthyridines base.
In one embodiment of present application, R1, R2, R4, R5 and R6 to R13 of chemical formula 1 can be each independently For hydrogen or deuterium.
In one embodiment of present application, R1, R2, R3, R5 and R6 to R13 of chemical formula 1 can be each independently For hydrogen or deuterium.
In one embodiment of present application, R, R' and R " of chemical formula 1 are same or different to each other, and can respectively solely It is on the spot hydrogen；The C for being substituted or being unsubstituted1To C60Alkyl；Or the C for being substituted or being unsubstituted6To C60Aryl.
In another embodiment, R, R' of chemical formula 1 and R " are same or different to each other, and can be each independently through taking Generation or the C being unsubstituted1To C40Alkyl；Or the C for being substituted or being unsubstituted6To C40Aryl.
In another embodiment, R, R' of chemical formula 1 and R " are same or different to each other, and can be each independently C6Extremely C40Aryl.
In another embodiment, R, R' of chemical formula 1 and R " are same or different to each other, and can be each independently benzene Base.
In the present specification, term " be substituted or be unsubstituted " mean via following persons composition group in select one or Multiple substituent groups replace: deuterium；Halogen；-CN；C1To C60Alkyl；C2To C60Alkenyl；C2To C60Alkynyl；C3To C60Naphthenic base；C2Extremely C60Heterocyclylalkyl；C6To C60Aryl；C2To C60Heteroaryl；-SiRR'R"；- P (=O) RR'；C1To C20Alkylamino radical；C6To C60Virtue Amido；And C2To C60Heteroaryl amido, or be unsubstituted, or the two through being bonded in above-mentioned substituent group or taking greater than the two Replace for base, or be substituted, or is connected by selected in above-mentioned substituent group two kinds or taken greater than the substituent group of two kinds of substituent groups Generation, or be unsubstituted.For example, " substituent group for connecting two or more substituent groups " may include xenyl.In other words, Xenyl can be aryl, or may be interpreted as the substituent group of two phenyl of connection.Additional substituents can be further substituted.R, R' with And R " is same or different to each other, and is each independently hydrogen；Deuterium；-CN；The C for being substituted or being unsubstituted1To C60Alkyl；Through taking Generation or the C being unsubstituted3To C60Naphthenic base；The C for being substituted or being unsubstituted6To C60Aryl；Or be substituted or be unsubstituted C2To C60Heteroaryl.
According to one embodiment of present application, " be substituted or be unsubstituted " is meaned via deuterium, halogen ,-CN, SiRR' R ", P (=O) RR', C1To C20Straight chain or branched-chain alkyl, C6To C60Aryl and C2To C60It is selected in the group of heteroaryl composition One or more substituent groups replace, or be unsubstituted, and
R, R' and R " is same or different to each other, and is each independently hydrogen；Deuterium；-CN；It is unsubstituted or through deuterium, halogen Base ,-CN, C1To C20Alkyl, C6To C60Aryl and C2To C60The C that heteroaryl replaces1To C60Alkyl；Be unsubstituted or through deuterium, Halogen ,-CN, C1To C20Alkyl, C6To C60Aryl and C2To C60The C that heteroaryl replaces3To C60Naphthenic base；It is unsubstituted or passes through Deuterium, halogen ,-CN, C1To C20Alkyl, C6To C60Aryl and C2To C60The C that heteroaryl replaces6To C60Aryl；Or it is unsubstituted Or through deuterium, halogen ,-CN, C1To C20Alkyl, C6To C60Aryl and C2To C60The C that heteroaryl replaces2To C60Heteroaryl.
Term " substitution ", which means to be bonded to the hydrogen atom of the carbon atom of compound, becomes another substituent group, and the position of substitution is not It is restricted, as long as it is the position that is substituted of hydrogen atom, that is, the substitutive position of substituent group, and takes when two or greater than two When replacing for base, two or greater than two substituent groups can be same or different to each other.
In the present specification, the halogen can be fluorine, chlorine, bromine or iodine.
In the present specification, the alkyl includes straight chain or branched chain with 1 to 60 carbon atom, and can further be passed through Other substituent groups replace.The carbon atom number of alkyl can be 1 to 60, in specific words 1 to 40 and more specifically 1 to 20.It is specific Example may include (but being not limited to) methyl, ethyl, propyl, n-propyl, isopropyl, butyl, normal-butyl, isobutyl group, tert-butyl, primary Butyl, 1- methyl-butvl, 1- Ethyl-butyl, amyl, n-pentyl, isopentyl, neopentyl, tertiary pentyl, hexyl, n-hexyl, 1- Methyl amyl, 2- methyl amyl, 4- methyl -2- amyl, 3,3- dimethylbutyl, 2- ethyl-butyl, heptyl, n-heptyl, 1- first Base hexyl, cyclopentyl-methyl, cyclohexyl methyl, octyl, n-octyl, t-octyl, 1- methylheptyl, 2- ethylhexyl, 2- propyl Amyl, n-nonyl, 2,2- dimethyl heptyl, 1- Ethyl-propyl, 1,1- Dimethyl-propyl, isohesyl, 2- methyl amyl, 4- first Base hexyl, 5- methylhexyl and similar group.
In the present specification, alkenyl includes the straight chain or branched chain with 2 to 60 carbon atoms, and can be further through other Substituent group replaces.The carbon atom number of alkenyl can be 2 to 60, in specific words 2 to 40 and more specifically 2 to 20.Its specific example May include (but being not limited to) vinyl, 1- acrylic, isopropenyl, 1- cyclobutenyl, 2- cyclobutenyl, 3- cyclobutenyl, 1- pentenyl, 2- pentenyl, 3- pentenyl, 3-methyl-1-butene base, 1,3- butadienyl, allyl, 1- phenyl vinyl -1- base, 2- benzene Base vinyl -1- base, 2,2- diphenylacetylene -1- base, 2- phenyl -2- (naphthalene -1- base) vinyl -1- base, 2,2- bis- (two Phenyl -1- base) vinyl -1- base, stilbene radicals, styryl and similar group.
In the present specification, alkynyl includes the straight chain or branched chain with 2 to 60 carbon atoms, and can be further through other Substituent group replaces.The carbon atom number of alkynyl can be 2 to 60, in specific words 2 to 40 and more specifically 2 to 20.
In the present specification, naphthenic base includes the monocycle or polycyclic with 3 to 60 carbon atoms, and can be further through other Substituent group replaces.Herein, polycyclic to mean a kind of group, the group middle ring alkyl be connected directly to other cyclic groups or It is condensed with other cyclic groups.Herein, other cyclic groups can be naphthenic base, but also can be different types of cyclic group Group, such as Heterocyclylalkyl, aryl and heteroaryl.The carbon number of the naphthenic base can be 3 to 60, in specific words 3 to 40 and have more The 5 to 20 of body speech.Its specific example may include (but being not limited to) cyclopropyl, cyclobutyl, cyclopenta, 3- methylcyclopentyl, 2,3- Dimethylcyclopentyl, cyclohexyl, 3- methylcyclohexyl, 4- methylcyclohexyl, 2,3- Dimethylcyclohexyl, 3,4,5- front three basic ring Hexyl, 4- tert-butylcyclohexyl, suberyl, cyclooctyl and similar group.
In the present specification, Heterocyclylalkyl includes being used as heteroatomic O, S, Se, N or Si, including have 2 to 60 carbon originals The monocycle or polycyclic of son, and can further replace through other substituent groups.Herein, polycyclic to mean a kind of group, the group Middle Heterocyclylalkyl is connected directly to other cyclic groups or condensed with other cyclic groups.Herein, other cyclic groups can It for Heterocyclylalkyl, but also can be different types of cyclic group, such as naphthenic base, aryl and heteroaryl.The Heterocyclylalkyl Carbon atom number can be 2 to 60, in specific words 2 to 40 and more specifically 3 to 20.
In the present specification, aryl includes the monocycle or polycyclic with 6 to 60 carbon atoms, and can further be taken through other Replace for base.Herein, polycyclic to mean a kind of group, in the group aryl be connected directly to other cyclic groups or and its His cyclic group is condensed.Herein, other cyclic groups can be aryl, but also can be different types of cyclic group, such as Naphthenic base, Heterocyclylalkyl and heteroaryl.Aryl includes spiro-cyclic groups.The carbon atom number of aryl can be 6 to 60, in specific words 6 To 40 and more specifically 6 to 25.The specific example of aryl may include (but being not limited to) phenyl, xenyl, terphenyl base, naphthalene Base, Qu Ji, phenanthryl, base, Fluorene anthryl, joins sub- triphenyl, propylene conjunction naphthalene, pyrenyl, thick four benzene base, thick five phenyl, Fluorene at anthryl Base, indenyl, acenaphthenyl, benzo Fluorene base, spiral shell connection Fluorene base, 2,3- dihydro -1H- indenyl, its condensed ring and similar group.
In the present specification, spiro-cyclic groups be include the group of spirane structure, and can have 15 to 60 carbon atoms.Citing For, spiro-cyclic groups may include a kind of structure, in the structure 2,3- dihydro -1H- indenyl or cyclohexyl loop coil be bonded to Fluorene base.Specifically, following spiro-cyclic groups may include having following structure any one of group of formula.
In the present specification, heteroaryl includes being used as heteroatomic O, S, Se, N or Si, including have 2 to 60 carbon atoms Monocycle or polycyclic, and can further replace through other substituent groups.Herein, polycyclic to mean a kind of group, in the group Heteroaryl is connected directly to other cyclic groups or condensed with other cyclic groups.Herein, other cyclic groups can be miscellaneous Aryl, but also can be different types of cyclic group, such as naphthenic base, Heterocyclylalkyl and aryl.The carbon atom number of heteroaryl It can be 2 to 60, in specific words 2 to 40 and more specifically 3 to 25.The specific example of heteroaryl may include (but being not limited to) pyridine Base, pyrrole radicals, pyrimidine radicals (pyrimidyl group), pyridazinyl (pyridazinyl group), furyl (furanyl Group), thienyl, imidazole radicals, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, triazolyl, furan a word used for translation base, evil Mutter base, thio piperazine of di azoly, thiadiazolyl group, dithiazole base, tetrazole radical, piperazine is muttered base, diazine (diazinyl group), oxazines Base, thiazinyl, dioxy how base (dioxynyl), triazine radical, tetrazine base, quinolyl, isoquinolyl, quinazolyl, isoquinoline oxazoline Base, quinolizine quinoline base (qninozolinyl), naphthyridines base (naphthyridyl group), acridinyl, coffee piperidinyl, imidazopyridine Base (imidazopyridinyl group), phthalazinyl, three a word used for translation indenyls (triazaindene group), indyl, Yin Diindyl piperazine base, benzothiazolyl, benzoxazolyl, benzimidazolyl, benzothienyl, benzofuranyl, dibenzothiophene, two Benzofuranyl, carbazyl, benzo carbazole base, dibenzo-carbazole base, coffee piperazine base, dibenzo Silole (dibenzosilole group), spiral shell two (dibenzo Silole) base, dihydro coffee piperazine base (dihydrophenazinyl Group), coffee oxazines base, phenanthridinyl (phenanthridyl group), thienyl, imidazo [1,2-a] pyridine, indoles be simultaneously [2,3-a] carbazyl, indoles simultaneously [2,3-b] carbazyl, indolinyl, 10,11- dihydro-dibenzo [b, f] azepines base, Acridan base, luxuriant and rich with fragrance anthracene azine (phenanthrazinyl), thiophene phenazinyl (phenothiathiazinyl), phthalazines Base, naphthyridines base (naphthylidinyl group) coffee quinoline base, benzo [c] [1,2,5] thiadiazolyl group, 5,10- dihydrobenzo [b, E] [1,4] aza-silicon quinoline (5,10-dihydrobenzo [b, e] [1,4] azasilinyl), pyrazolo [1,5-c] quinazolyl, Pyrido [1,2-b] indazolyl, pyrido [1,2-a] imidazo [1,2-e] indolinyl, 5,11- dihydro indeno [1,2-b] Carbazyl (5,11-dihydroindeno [1,2-b] carbazolyl group) and similar group.
In the present specification, it is selected in the group that amido can be made of following persons: monoalkyl amido；Monoarylamine base；It is single miscellaneous Arylamine group；-NH2；Dialkyl amino；Diaryl amido；Di (hetero) arylamine group；Alkylaryl amido；Miscellaneous alkyl aryl amido； And aryl heteroaryl amido, although and carbon atom number not by its specific limitation, preferably 1 to 30.The amido it is specific Example may include (but being not limited to) methylamino, dimethylamino, ethylamino-, diethylin, anilino-, naphthylamine base, benzidion, two Benzidion, anthranylamine base (anthracenylamine group), 9- methyl-anthranylamine base, hexichol amido, phenylnaphthalene amido, two Toluene amido (ditolylamine group), phenyltoluene amido, triphenylamine base, biphenyl naphthylamine base, phenyl benzidion, connection Benzene Fluorene amido, phenyl Asia triphenyl amido (phenyltriphenylenylamine group), xenyl Asia triphenyl amido And similar group.
In the present specification, arlydene means tool there are two the aryl in bond site, that is, bivalent groups.Except respectively two Other than valence group, the description presented above as described in aryl can be applied to this.In addition, inferior heteroaryl means tool, there are two bonds The heteroaryl in site, that is, bivalent group.In addition to respectively bivalent group, the description presented above as described in heteroaryl can Applied to this.
According to one embodiment of present application, chemical formula 1 can be indicated by any one of following compound, but be not limited to This.
In addition, can be synthesized by the structure that various substituent groups are introduced to chemical formula 1 with the only of introduced substituent group The compound of characteristic.For example, by the way that substituent group (is typically used as the hole injection layer for manufacturing organic light emitting apparatus Material, hole transport layer material, emitting layer material, electronics transfer layer material and charge generation layer material) it is introduced to core knot Structure can synthesize the material of condition needed for meeting each organic material layer.
In addition, by the structure that various substituent groups are introduced to chemical formula 1 band gap can be finely controlled, and simultaneously, strengthen The characteristic of interface between organic material, and material application is diversifiedly variable.
Meanwhile heterocyclic compound has splendid thermal stability under compared with high glass transition temperature (Tg).Thermal stability this Class, which improves, becomes an important factor for providing driving stability to device.
It can be reacted and be prepared by multi-step chemical according to the heterocyclic compound of one embodiment of present application.One is prepared first A little intermediate compounds, and the compound of chemical formula 1 can be prepared by the intermediate compound.More precisely, according to present application The heterocyclic compound of one embodiment can be prepared based on the preparating example being described below.
Another embodiment of present application provides organic light emitting apparatus, and the organic light emitting apparatus includes by 1 table of chemical formula The heterocyclic compound shown.
In addition to using heterocyclic compound as described above to form one or more organic material layers, it can be used general organic Method for producing light-emitting device and material manufacture the organic light emitting apparatus of one embodiment according to present application.
When manufacturing organic light emitting apparatus, heterocyclic compound can be made to be formed as by solution coating method and vacuum deposition method Organic material layer.Herein, solution coating method means (but being not limited to) spin coating, dip-coating, ink jet printing, screen printing, is sprayed Method, roll coating process and similar approach.
Specifically, including anode, cathode and setting according to the organic light emitting apparatus of one embodiment of present application One or more organic material layers between anode and cathode, wherein the one layer or more of organic material layer includes by 1 table of chemical formula The heterocyclic compound shown.
Fig. 1 to Fig. 3 illustrates the electrode and organic material of the organic light emitting apparatus of one embodiment according to present application The lamination order of layer.However, the range of present application is not limited to these attached drawings, and organic light emitting apparatus as known in the art Structure also can be used in present application.
Fig. 1 illustrates organic light emitting apparatus, Anodic (200), organic material layer (300) and cathode (400) pantostrat Together on substrate (100).However, the structure is not limited to this class formation, and as illustrated in figure 2, organic light emission also can get Device, cathode, organic material layer and anode continuous lamination are on substrate in the organic light emitting apparatus.
Fig. 3 illustrates that organic material layer is the case of multilayer.Organic light emitting apparatus according to Fig. 3 includes hole injection layer (301), hole transport layer (302), luminescent layer (303), hole blocking layer (304), electronics transfer layer (305) and electron injection Layer (306).However, the range of present application is not limited to this kind of laminated construction, and optionally, in addition to the light emitting layer its can not included His layer, and can further include other necessary function layers.
In addition, including anode, cathode according to the organic light emitting apparatus of one embodiment of present application and being set to sun Two between pole and cathode or it is greater than two laminations, wherein described two or greater than two laminations include shining each independently Layer, and charge generation layer is contained in described two or is greater than between two laminations, and charge generation layer includes being indicated by chemical formula 1 Heterocyclic compound.
In addition, include anode according to the organic light emitting apparatus of one embodiment of present application, be set on anode One lamination, and including the first luminescent layer, the charge generation layer being set on the first lamination, be set on charge generation layer second Lamination, and including the second luminescent layer and the cathode being set on the second lamination.Herein, charge generation layer may include by changing The heterocyclic compound that formula 1 indicates.In addition, furthermore the first lamination and the second lamination can include described above each independently One or more types hole injection layer, hole transport layer, hole blocking layer, electronics transfer layer, electron injecting layer and class Like person.
Charge generation layer can be N-type charge generation layer, and in addition to the heterocyclic compound indicated by chemical formula 1, charge is produced Furthermore generating layer can include dopant as known in the art.
Such as according to the organic light emitting apparatus of one embodiment of present application, schematically illustrate in Fig. 4 folded with 2- The organic light emitting apparatus of layer gang type structure.
Herein, the first electronic barrier layer, the first hole blocking layer described in Fig. 4, the second hole blocking layer and Fellow can be not included in some cases.
In addition to one or more layers in organic material layer include the heterocyclic compound indicated by chemical formula 1, this can be used Known method and material manufacture the organic light emitting apparatus according to this specification in field.
The one or more of the organic material layer of organic light emitting apparatus may be separately formed by the heterocyclic compound that chemical formula 1 indicates Layer.However, optionally, the heterocyclic compound indicated by chemical formula 1 can be mixed to form organic material layer with other materials.
The heterocyclic compound indicated by chemical formula 1 can be used as the material of charge generation layer in organic light emitting apparatus.
The heterocyclic compound indicated by chemical formula 1 can be used as in organic light emitting apparatus electronics transfer layer, hole blocking layer, Luminescent layer or the material of fellow.As an example, the heterocyclic compound indicated by chemical formula 1 can in organic light emitting apparatus Material as electronics transfer layer, hole transport layer or luminescent layer.
In addition, the heterocyclic compound indicated by chemical formula 1 can be used as the material of luminescent layer in organic light emitting apparatus.As One example, the heterocyclic compound indicated by chemical formula 1 can be used as the phosphorescent light body material of luminescent layer in organic light emitting apparatus.
In the organic light emitting apparatus according to one embodiment of present application, the jeterocyclic chemistry except chemical formula 1 is illustrated below The material other than object is closed, however, these materials are only the range reached the purpose of explanation and be not used in limitation present application, and can Replace with material as known in the art.
Can be used with relatively large work function material as anode material, and can be used transparent conductive oxide, Metal, conducting polymer or similar material.The specific example of the anode material including (but not limited to): metal, such as vanadium, Chromium, copper, zinc and gold or its alloy；Metal oxide, such as zinc oxide, indium oxide, tin indium oxide (ITO) and indium oxide Zinc (IZO)；The combination of metal and oxide, such as ZnO:Al or SnO2:Sb；Conducting polymer, such as poly- (3- methyl chemical combination Object), poly- [3,4- (two oxygroup of ethylidene -1,2-) thiophene] (PEDOT), polypyrrole and polyaniline.
It can be used the material with relatively small work function as cathode material, and metal can be used, metal oxide, lead Electric polymer or similar material.The particular instance of cathode material include metal, such as, magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, Gadolinium, aluminium, silver, tin and lead or its alloy；Sandwich, such as, LiF/Al or LiO2/ Al with and so on, but not It is limited to this.
It can be used known hole-injecting material as hole-injecting material, and phthalocyanine compound for example can be used, such as Copper phthalocyanine disclosed in U.S. Patent No. 4,356,429；Or star burst amine derivative, such as it is described in document [advanced material Expect (Advanced Material), page 6,677 (p.677) (1994)] in three (4- hydrazine formoxyl -9- base phenyl) amine (TCTA), 4,4', 4 "-three [phenyl (tolyl) amido] triphenylamines (m-MTDATA) or [4- (the 3- aminomethyl phenyl of 1,3,5- tri- Phenyl amido) phenyl] benzene (m-MTDAPB)；Conducting polymer with solubility, polyaniline/dodecyl benzene sulfonic acid (polyaniline/dodecylbenzenesulfonic acid), poly- (3,4- Ethylenedioxy Thiophene)/poly- (4- styrene Sulfonic acid rouge) (poly (3,4-ethylenedioxy thiophene)/poly (4-styrenesulfonate)), polyaniline/camphor tree Brain sulfonic acid (polyaniline/camphor sulfonic acid) or polyaniline/poly- (4- styrene-sulphonic acid ester) (polyaniline/poly(4-styrene-sulfonate))；And similar material.
Pyrazoline derivative, aromatic amino-derivative, diphenyl ethylene derivatives, triphenyl diamine derivative and class can be used Like material as hole transport material, and low molecule or high molecular material also can be used.
Can be used the metal misfit objects of oxadiazole derivatives, anthraquinone bismethane (anthraquinodimethane) and its Derivative, benzoquinones and its derivative, naphthoquinones (naphthoquinone) and its derivative, anthraquinone and its derivative, four Cyanogen anthraquinone bismethane and its derivative, Fluorene ketone derivatives, two acrylonitrile of diphenyl and its derivative, diphenoquinone, 8-hydroxyquinoline and its derivative and similar material, and also can be used high molecular material and low molecule material as electricity Sub- material for transfer.
As the example of electron injection material, LiF is commonly used in this field, however, present application is without being limited thereto.
Can be used glow, the material of green light or blue light, and optionally by two kinds or two kinds of luminescent materials mixing can be greater than And used as luminescent material.In addition, also can be used fluorescent material as luminescent material, however, phosphor material also can be used. It can be used alone by being bonded the electronics being injected separately into from anode and cathode and hole come luminous material as luminous Material, however, the material with material of main part and dopant material (simultaneously participating in luminous) also can be used.
It can be top light emitting according to the organic light emitting apparatus of one embodiment of present application depending on material used Type, bottom emission type or dual-side luminescent type.
Also it can be used in organic electronic device according to the heterocyclic compound of one embodiment of present application, the Organic Electricity Sub-device includes with the principle of similitude for organic solar batteries, the organic photoconductor, organic transistor in organic light emitting apparatus And fellow.
Mode of the invention
Hereinafter, this specification will be described in more detail referring to example, however, these are only the mesh for reaching explanation , and the range of present application is without being limited thereto.
<example>
The preparation of<preparating example 1>compound 2
1) preparation of compound 2-1
By aniline (aniline) (19.8ml, 213mmol) and acetic acid sodium trihydrate (sodium acetate Trihydrate) (26.4g, 318mol) is added to the bromo- 2- nitrobenzene (Isosorbide-5-Nitrae-dibromo-2- of compound Isosorbide-5-Nitrae-two Nitrobenzene) after (30g, 106mmol), obtained material is stirred 30 minutes at 80 DEG C and then at 160 DEG C next time Stream continues 72 hours.After the reaction was completed, obtained material is cooled to room temperature, and is extracted with distilled water and EA.With anhydrous MgSO4 After dry organic layer, remove solvent using rotary evaporator, and use column chromatography use methylene chloride and hexane as Solvent purifies obtained material, to obtain target compound 2-1 (31g, 99%).
2) preparation of compound 2-2
After compound 2-1 (31g, 105mmol) is dissolved in THF (210ml), addition is dissolved in thereto Two sulphonic acid sodiums (sodium dithionite) (93g, 525mmol) in 370ml distilled water, and by obtained material in room temperature Lower stirring 12 hours.After the reaction was completed, obtained material is extracted with distilled water and EA.With anhydrous MgSO4After dry organic layer, make Solvent is removed with rotary evaporator, and obtains target compound 2-2 (28g, 100%) in the case where not being further purified.
3) preparation of compound 2-3
After compound 2-2 (28g, 106mmol) is dissolved in nitrobenzene (nitrobenzene), by obtained material Reflux continues 6 hours at 180 DEG C.After the reaction was completed, be evaporated in vacuo obtained material to remove nitrobenzene (nitrobenzene), And it is then extracted with distilled water and EA.With anhydrous MgSO4After dry organic layer, solvent is removed using rotary evaporator, and Column chromatography methylene chloride and hexane is used to purify obtained material as solvent, to obtain target compound 2-3 (15g, 40%).
4) preparation of compound 2-4
After compound 2-3 (15g, 43.0mmol) is dissolved in Isosorbide-5-Nitrae-dioxanes (Isosorbide-5-Nitrae-dioxane), add thereto Add bis- (pinacol foundation) two boron (bis (pinacolato) diboron) (21g, 86.0mmol), Pd (dppf) Cl2(1.6g, 2.15mmol) and potassium acetate (potassium acetate) (12.7g, 129mmol), and obtained material is stirred at 110 DEG C It mixes 2 hours.After the reaction was completed, obtained material is extracted with distilled water and EA.With anhydrous MgSO4After dry organic layer, rotation is used Rotatable evaporator removes solvent, and target compound 2-4 (9.5g, 56%) is obtained in the case where not being further purified.
5) preparation of compound 2-5
Compound 2-4 (9.5g, 23.0mmol) is being dissolved in toluene (toluene), EtOH and H2After in O, to Wherein add 2- bromaniline (2-bromoaniline) (4.9g, 28.8mmol), Pd (PPh3)4(1.4g, 1.2mmol) and K2CO3(10.0g, 72.0mmol), and obtained material is stirred 6 hours at 110 DEG C.After the reaction was completed, obtained material is cooling It is extracted to room temperature, and with distilled water and EA.With anhydrous MgSO4After dry organic layer, solvent is removed using rotary evaporator, And column chromatography methylene chloride and hexane is used to purify obtained material as solvent, to obtain target compound 2-5 (7.1g, 82%).
6) preparation of compound 2-6
After compound 2-5 (7.1g, 19.6mmol) is dissolved in THF, 4- bromobenzene first is added thereto at 0 DEG C Acyl chloride (4-bromobenzoyl chloride) (3.8ml, 29.4mmol) and TEA (8.1ml, 58.8mmol), and Obtained material is stirred at room temperature 2 hours.After the reaction was completed, EA and distilled water are added to reactor to be used to solidify, and The solid generated is collected to obtain target compound 2-6 (11g, 100%).
7) preparation of compound 2-7
After compound 2-6 (11g, 20.2mmol) is dissolved in nitrobenzene (nitrobenzene), add thereto Add POCl3(1.9ml, 20.2mmol), and obtained material is stirred 18 hours at 150 DEG C.After the reaction was completed, institute is evaporated in vacuo Substance is obtained to remove nitrobenzene (nitrobenzene), is then cooled to room temperature, and extracted with distilled water and EA.With anhydrous MgSO4After dry organic layer, solvent is removed using rotary evaporator, and use column chromatography methylene chloride and hexane Obtained material is purified as solvent, to obtain target compound 2-7 (7.4g, 69%).
8) preparation of compound 2-8
After compound 2-7 (7.4g, 14.1mmol) is dissolved in Isosorbide-5-Nitrae-dioxanes (Isosorbide-5-Nitrae-dioxane), add thereto Add bis- (pinacol foundation) two boron (bis (pinacolato) diborone), Pd (dppf) Cl2And potassium acetate (potassium Acetate it), and by obtained material is stirred 2 hours at 110 DEG C.After the reaction was completed, gains are extracted with distilled water and EA Matter.With anhydrous MgSO4After dry organic layer, solvent is removed using rotary evaporator, and in the case where not being further purified Obtain target compound 2-8 (8.0g, 100%).
9) preparation of compound 2
The bromo- 10- phenylanthracene (9-bromo-10- of 9- is being added to compound 2-8 (8.0g, 14.1mmol) Phenylanthracene) (5.6g, 16.9mmol), Pd (PPh3)4(0.8g, 0.71mmol), K2CO3(5.8g, 42.3mmol) And toluene (tolene)/EtOH/H2After O, obtained material is stirred 2 hours at 110 DEG C.After the reaction was completed, by gained Substance is cooled to room temperature, and is extracted with distilled water and EA.With anhydrous MgSO4After dry organic layer, rotary evaporator is used Solvent is removed, and column chromatography methylene chloride and hexane is used to purify obtained material as solvent, to obtain target Compound 2 (8.4g, 86%).
The preparation of<preparating example 2>compound 5
After compound 2-7 (7.1g, 13.5mmol) is dissolved in THF, slowly add dropwise thereto at -78 DEG C Add 2.5M n-BuLi (7.0ml, 17.6mmol), and obtained material is stirred 30 minutes.Three methylphosphine of chlordiphenyl is added thereto (3.3ml, 17.6mmol), and obtained material is stirred 1 hour.After the reaction was completed, methanol is added thereto, and by obtained material Stirring 1 hour, and then extracted with distilled water and EA.With anhydrous MgSO4Dry organic layer, and then use rotary evaporator Remove solvent.The liquid of concentration is dissolved by addition methylene chloride (150ml), and adds hydrogen peroxide thereto (hydrogen peroxide) (7.0ml), and obtained material is stirred at room temperature 3 hours.After the reaction was completed, distilled water is used And EA extracts obtained material.With anhydrous MgSO4Dry organic layer, and then solvent is removed using rotary evaporator.Pass through Toluene and heating are added to dissolve obtained material, and is then recrystallized to obtain target compound 5 (7.1g, 81%).
The preparation of<preparating example 3>compound 10
The bromo- 10- phenylanthracene (9-bromo-10- of 9- is being added to compound 2-8 (8.0g, 14.1mmol) Phenylanthracene) (5.6g, 16.9mmol), Pd (PPh3)4(0.8g, 0.71mmol), K2CO3(5.8g, 42.3mmol) And toluene (tolene)/EtOH/H2After O, obtained material is stirred 2 hours at 110 DEG C.After the reaction was completed, by gained Substance is cooled to room temperature, and is extracted with distilled water and EA.With anhydrous MgSO4After dry organic layer, rotary evaporator is used Solvent is removed, and column chromatography methylene chloride and hexane is used to purify obtained material as solvent, to obtain target Compound 10 (8.4g, 86%).
The preparation of<preparating example 4>compound 11
Except using the bromo- 4,6- diphenyl -1,3,5- triazine (2-bromo-4,6-diphenyl-1,3,5-triazine) of 2- Except the bromo- 10- phenylanthracene (9-bromo-10-phenylanthracene) of 9-, with the compound 2 in preparating example 1 Identical mode obtains target compound 11.
The preparation of<preparating example 5>compound 15
Except using bromo- 4,6- bis- (naphthalene -2- the base) -1,3,5- triazine (2-bromo-4,6-di (naphthalen-2- of 2- Yl) -1,3,5-triazine) replace the bromo- 10- phenylanthracene (9-bromo-10-phenylanthracene) of 9- except, using with The identical mode of compound 2 in preparating example 1 obtains target compound 15.
The preparation of<preparating example 6>compound 25
Except using 4- ([1,1'- biphenyl] -4- base) the bromo- 6- phenyl pyrimidine of -2- (4- ([1,1'-biphenyl] -4-yl) - 2-bromo-6-phenylpyrimidine) replace the bromo- 10- phenylanthracene (9-bromo-10-phenylanthracene) of 9- it Outside, target compound 25 is obtained using mode identical with the compound 2 in preparating example 1.
The preparation of<preparating example 7>compound 55
Except using 4- ([1,1'- biphenyl] -4- base) -2- bromine quinazoline (4- ([1,1'-biphenyl] -4-yl) -2- Bromoquinazoline) replace the bromo- 10- phenylanthracene (9-bromo-10-phenylanthracene) of 9- except, with preparation The identical mode of compound 2 in example 1 obtains target compound 55.
The preparation of<preparating example 8>compound 70
Except use the bromo- 2,4,6- triphen yl pyrimidines (5-bromo-2,4,6-triphenylpyrimidine) of 5- replace 9- Except bromo- 10- phenylanthracene (9-bromo-10-phenylanthracene), with identical with the compound 2 in preparating example 1 Mode obtains target compound 70.
The preparation of<preparating example 9>compound 89
Except use the bromo- 1,10- coffee quinoline (2-bromo-1,10-phenanthroline) of 2- replace the bromo- 10- phenylanthracene of 9- Except (9-bromo-10-phenylanthracene), target is obtained in a manner of identical with the compound 2 in preparating example 1 Compound 89.
The preparation of<preparating example 10>compound 94
Except using bromo- 2- phenylimidazole [1,2-a] the pyridine (- bromo-2-phenylimidazo [1,2-a] of 6- Pyridine) replace the bromo- 10- phenylanthracene (9-bromo-10-phenylanthracene) of 9- except, with in preparating example 1 The identical mode of compound 2 obtain target compound 94.
The preparation of<preparating example 11>compound 101
Except using 1- (4- bromophenyl) -2- ethyl -1H- benzo [d] imidazoles (1- (4-bromophenyl) -2-ethyl- 1H-benzo [d] imidazole) replace the bromo- 10- phenylanthracene (9-bromo-10-phenylanthracene) of 9- except, with The identical mode of compound 2 in preparating example 1 obtains target compound 101.
The preparation of<preparating example 12>compound 104
Except use 2- (4- bromophenyl) benzo [d] thiazole (2- (4-bromophenyl) benzo [d] thiazole) replace Except the bromo- 10- phenylanthracene (9-bromo-10-phenylanthracene) of 9-, with identical as the compound 2 in preparating example 1 Mode obtain target compound 104.
The preparation of<preparating example 13>compound 126
Except use 3- bromoquinoline (3-bromoquinoline) replace the bromo- 10- phenylanthracene (9-bromo-10- of 9- Phenylanthracene except), target compound 126 is obtained in a manner of identical with the compound 2 in preparating example 1.
The preparation of<preparating example 14>compound 131
Except use the bromo- 2,2'- binaphthalene (6-bromo-2,2'-binaphthalene) of 6- replace the bromo- 10- phenylanthracene of 9- Except (9-bromo-10-phenylanthracene), target is obtained in a manner of identical with the compound 2 in preparating example 1 Compound 131.
The preparation of<preparating example 15>compound 133
Except use 4- bromobenzylcyanide (4-bromobenzonitrile) replace the bromo- 10- phenylanthracene (9-bromo-10- of 9- Phenylanthracene except), target compound 133 is obtained in a manner of identical with the compound 2 in preparating example 1.
The preparation of<preparating example 16>compound 136
Except use 2- bromopyridine (2-bromopyridine) replace the bromo- 10- phenylanthracene (9-bromo-10- of 9- Phenylanthracene except), target compound 136 is obtained in a manner of identical with the compound 2 in preparating example 1.
The preparation of<preparating example 17>compound 152
Except using 3- (4- bromophenyl) -2- phenylimidazole [1,2-a] pyridine (3- (4-bromophenyl) -2- Phenylimidazo [1,2-a] pyridine) replace the bromo- 10- phenylanthracene (9-bromo-10-phenylanthracene) of 9- Except, target compound 152 is obtained in a manner of identical with the compound 2 in preparating example 1.
The preparation of<preparating example 18>compound 153
Except use 8- bromoquinoline (8-bromoquinoline) replace the bromo- 10- phenylanthracene (9-bromo-10- of 9- Phenylanthracene except), target compound 153 is obtained in a manner of identical with the compound 2 in preparating example 1.
The preparation of<preparating example 19>compound 154
1) preparation of compound 154-1
After compound 2-5 (30g, 83.0mmol) is dissolved in THF, 3- bromobenzene first is added thereto at 0 DEG C Acyl chloride (3-bromobenzoyl chloride) (16.5ml, 1.5eq) and TEA (34.5ml, 3.0eq.), and will Obtained material is stirred at room temperature 2 hours.After the reaction was completed, EA and distilled water are added to reactor to be used to solidify, and received Collect the solid generated to obtain target compound 154-1 (44g, 97%).
2) preparation of compound 154-2
After compound 2-6 (44g, 80.8mmol) is dissolved in nitrobenzene (nitrobenzene), add thereto Add POCl3(7.5ml, 1.0eq.), and obtained material is stirred 18 hours at 150 DEG C.After the reaction was completed, vacuum distillation gained Substance is then cooled to room temperature to remove nitrobenzene (nitrobenzene), and is extracted with distilled water and EA.With anhydrous MgSO4 After dry organic layer, remove solvent using rotary evaporator, and use column chromatography use methylene chloride and hexane as Solvent purifies obtained material, to obtain target compound 154-2 (30g, 71%).
3) preparation of compound 154-3
After compound 2-7 (30g, 57.0mmol) is dissolved in Isosorbide-5-Nitrae-dioxanes, bis- (pinacol roots are added thereto Base) two boron (bis (pinacolato) diborone), Pd (dppf) Cl2And potassium acetate (potassium acetate), and Obtained material is stirred 2 hours at 110 DEG C.After the reaction was completed, obtained material is extracted with distilled water and EA.With anhydrous MgSO4After dry organic layer, solvent is removed using rotary evaporator, and targeted is obtained in the case where not being further purified It closes object 154-3 (29g, 89%).
4) preparation of compound 154
By (4- bromophenyl) diphenyl phosphine oxide ((4-bromophenyl) diphenylphosphine oxide) (5.5g, 15.3mmol), Pd (PPh3)4(0.8g, 0.71mmol), K2CO3(5.8g, 42.3mmol) and toluene (tolene)/ EtOH/H2O is added to after compound 154-1 (8.0g, 14.1mmol), and obtained material is stirred 2 hours at 110 DEG C.Instead After the completion of answering, obtained material is cooled to room temperature, and is extracted with distilled water and EA.With anhydrous MgSO4After dry organic layer, make With rotary evaporator remove solvent, and use column chromatography methylene chloride and hexane as solvent purify obtained by production Object, to obtain target compound 154 (8.5g, 83%).
The preparation of<preparating example 20>compound 155
Except using the bromo- 4,6- diphenyl -1,3,5- triazine (2-bromo-4,6-diphenyl-1,3,5-triazine) of 2- Except (4- bromophenyl) diphenyl phosphine oxide ((4-bromophenyl) diphenylphosphine oxide), with The identical mode of compound 154 in preparating example 19 obtains target compound 155.
The preparation of<preparating example 21>compound 156
Except using 9,9'- (the bromo- 1,3- phenylene of 5-) bis- (9H- carbazole) (9,9'- (5-bromo-1,3-phenylene) Bis (9H-carbazole)) replace (4- bromophenyl) diphenyl phosphine oxide ((4-bromophenyl) Diphenylphosphine oxide) except, targeted is obtained in a manner of identical with the compound 154 in preparating example 19 Close object 156.
The preparation of<preparating example 22>compound 158
Except using the chloro- 2,6- diphenylpyrimidin (4-chloro-2,6-diphenylpyrimidine) of 4- to replace (4- bromobenzene Base) except diphenyl phosphine oxide ((4-bromophenyl) diphenylphosphine oxide), with preparating example 19 In the identical mode of compound 154 obtain target compound 158.
The preparation of<preparating example 23>compound 161
Except using 4- ([1,1'- biphenyl] -4- base) -6- (4- chlorphenyl) -2- phenyl pyrimidine (4- ([1,1'- Biphenyl] -4-yl) -6- (4-chlorophenyl) -2-phenylpyrimidine) replace (4- bromophenyl) diphenylphosphine Except oxide ((4-bromophenyl) diphenylphosphine oxide), with the compound in preparating example 19 154 identical modes obtain target compound 161.
The preparation of<preparating example 24>compound 164
Except using 2- (4- bromophenyl) -9- phenyl -1,10- coffee quinoline (2- (4-bromophenyl) -9-phenyl-1,10- Phenanthroline (4- bromophenyl) diphenyl phosphine oxide ((4-bromophenyl) diphenylphosphine) is replaced Oxide except), target compound 164 is obtained in a manner of identical with the compound 154 in preparating example 19.
The preparation of<preparating example 25>compound 165
Except using 1- (4- bromophenyl) -2- ethyl -1H- benzo [d] imidazoles (1- (4-bromophenyl) -2-ethyl- 1H-benzo [d] imidazole) replace (4- bromophenyl) diphenyl phosphine oxide ((4-bromophenyl) Diphenylphosphine oxide) except, targeted is obtained in a manner of identical with the compound 154 in preparating example 19 Close object 165.
The prepare compound in a manner of identical with the preparating example, and synthesize qualification result and be showed in table 1 and table 2 In.
[table 1]
[table 2]
<experiment embodiment>
<experiment embodiment 1>
1) manufacture of organic light emitting apparatus
With distilled water ultrasonic clean glass substrate, ITO as film withThe thickness of (angstrom) is coated on the glass On substrate.After being cleaned with distilled water, substrate is cleaned with solvent (such as acetone, methanol and isopropanol) ultrasonic, then It is dry, and carry out UVO in the UV cleaner using UV and handle 5 minutes.Hereafter, substrate is transferred to plasma cleaner (PT), it carries out corona treatment and under vacuum to remove ITO work function and remaining film, and substrate is transferred to heat Depositing device is to be used for organic deposit.
On ito transparent electrode (anode), organic material is formed in two lamination WOLED (white-light organic light-emitting devices (white orgainc light emitting device)) in structure.For the first lamination, TAPC is deposited by thermal vacuum ExtremelyThickness be initially formed hole transport layer.After forming hole transport layer, the following thermal vacuum of luminescent layer is deposited on it On.It is deposited and FIrpic is adulterated 8% to TCz1 (main body) as blue phosphorescent dopantLuminescent layer.Electronics Transfer layer is configured to using TmPyPBAnd then by by Cs2CO3Doping 20% to compound described in the following table 3, Charge generation layer is configured to
For the second lamination, deposited by thermal vacuumThickness MoO3And it is initially formed hole injection layer.By by MoO3 Doping 20% to TAPC is simultaneously configured toAnd form hole transport layer (general layer), and then by TAPC deposit to? By by Ir (ppy)3(green phosphorescent dopant) adulterates 8% to TCz1 (main body), depositionLuminescent layer thereon after, make It is formed with TmPyPBElectronics transfer layer.Finally, passing through depositionThickness lithium fluoride (lithium fluoride: LiF), it is formed in electron injecting layer on electronics transfer layer, and then passes through depositionThick aluminium (Al) cathode, makes cathode It is formed on electron injecting layer, to manufacture organic light emitting apparatus.
Meanwhile 10-6~10-8It is all by the every kind of material vacuum sublimation purification manufactured for OLED under torr (support) Organic compound needed for manufacturing OLED device.
2) driving voltage and luminous efficiency of organic light emitting apparatus
For organic light emitting apparatus manufactured as above, electroluminescent hair is measured using the M7000 manufactured by McScience company Light light emitting (EL) feature, and by the measurement result, when standard luminosity is 3500cd/m2(candela/square metre) when, make T is measured with the life-span test system (M6000) manufactured by McScience company95.Measuring white light made according to the present invention has The driving voltage of machine light emitting device, luminous efficiency, the result such as institute's exhibition in table 3 of external quantum efficiency and hue coordinate (CIE) Show.
[table 3]
If the result of table 3 is shown, the charge generation layer material of white-light organic light-emitting device is stacked using 2- of the invention Organic light emitting apparatus compare comparative example 1 have compared with low driving voltage and improvement luminous efficiency.Specifically, recognizing Conjunction object 5,10,11,17,25,26,43,52,124 and 147 in driving, efficiency and is all significant splendid in terms of the service life.
The supposition of this kind of result the reason is that, be used as N-type charge generation layer (by special with appropriate length, intensity and plane Property framework of the present invention with can be formed with the appropriate heterocompound of metal bonding) the compound of the present invention doped with alkali metal Or alkaline-earth metal, in forming space state, and the interval by being created in N-type charge generation layer in N-type charge generation layer State is easy to be produced from the electron injection of p-type charge generation layer to electronics transfer layer.Therefore, p-type charge generation layer is successfully The electron injection and electronics transfer to N-type charge generation layer are carried out, and it is therefore contemplated that the driving voltage of organic light emitting apparatus drops It is low, and efficiency and service life are improved.
<experiment embodiment 2>
1) manufacture of organic light emitting apparatus
Respectively using trichloro ethylene, acetone, ethyl alcohol and distilled water, continuously ultrasonic is cleaned from the glass for being used for OLED Transparent electrode ito thin film 5 minutes of (being manufactured by Samsung-healthy and free from worry (Samsung-Corning)) acquisition, by the transparent electrode Ito thin film is placed in isopropanol and stores, and then uses.
Then, ito substrate is installed in the substrate folder of vacuum deposition device, and subsequent by 4,4', 4 "-three (N, N- (2- Naphthalene)-anilino-) terphenyl amine (4,4', 4 "-tris (N, N- (2-naphthyl)-phenylamino) triphenyl Amine:2-TNATA the vacuum chamber) being introduced in vacuum deposition device.
Then, the chamber is emptied, until the level of vacuum of chamber interior reaches 10-6Torr (support), and then by electric current Vacuum chamber is applied to so that 2-TNATA vaporization is to which deposition hasThe hole injection layer of thickness is on ito substrate.
By following N, bis- (Alpha-Naphthyl)-N, N'- diphenyl-the 4,4'- diamines of N'- (N, N'-bis (α-naphthyl)-N, N'-diphenyl-4,4'-diamine:NPB) it is introduced to the different chamber in vacuum deposition device, it applies a current to for steaming The room of hair has to deposit on hole injection layerThe hole transport layer of thickness.
After hole injection layer and hole transport layer as formed above, the blue emitting material having the following structure is deposited in it It is upper to be used as luminescent layer.Specifically, vacuum deposition in a vacuum chamber in vacuum deposition deviceThe H1 of thickness is (blue Color light emitting host material), and vacuum deposition relative to material of main part 5%D1 (blue-light-emitting dopant material) thereon.
Then, it depositsThe compound of the following structural formula E1 of thickness is as electronics transfer layer.
DepositionThe lithium fluoride (lithium fluoride:LiF) of thickness is used as electron injecting layer, and is formed The Al cathode of thickness, to manufacture OLED device.
Meanwhile 10-6~10-8It is all by the every kind of material vacuum sublimation purification manufactured for OLED under torr (support) Organic compound needed for manufacturing OLED device.
Except use the following table 4 compound replace compound E1 as electronics transfer layer in addition to, with identical with experiment embodiment 2 Mode manufacture OLED device.
2) driving voltage and luminous efficiency of organic light emitting apparatus
For organic light emitting apparatus manufactured as above, electroluminescent hair is measured using the M7000 manufactured by McScience company Light light emitting (EL) feature, and by the measurement result, when standard luminosity is 700cd/m2When, using by McScience public affairs The life-span test system (M6000) of manufacture is taken charge of to measure T95.Measure the drive of white-light organic light-emitting device made according to the present invention The result of voltage, luminous efficiency, external quantum efficiency and hue coordinate (CIE) is moved as shown in table 4.
[table 4]
If the result of table 4 is shown, using blue light organic emissive device of the invention electronics transfer layer material it is organic Light emitting device, which compares comparative example 3, has the luminous efficiency compared with low driving voltage and significantly improved and service life.Specifically, knowing Compound 5,10,11,17,25,26,43,52,124 and 147 is clipped in driving, efficiency and is all significant pole in terms of the service life Good.
The supposition of this kind of result the reason is that, when using the chemical combination of the present invention with appropriate length, intensity and flatness of the response When object is as electronics transfer layer, the compound in excitation state is generated by receiving electronics under specific circumstances, and in specific words, When the excitation state is formed in the miscellaneous framework sites of the compound, excitation energy is passed through in the miscellaneous framework sites being stimulated Stable state is transferred to before differential responses, and opposite stable compound can be in the case where not decomposing or destroying compound effectively Shift electronics.As reference, it is believed that when activated, those compounds with stable state be aryl or simultaneously benzene-like compounds or Polycyclic heterocompound.It is therefore contemplated that the compound of the present invention enhances electron transfer properties or improves stability, so that driving It is all splendid in terms of dynamic, efficiency and service life.

Claims (13)

1. a kind of heterocyclic compound indicated by following formula 1:
[chemical formula 1]
Wherein, in chemical formula 1,
At least one of R1 to R5 is by-(L1) p- (Z1) q expression, and remaining is hydrogen, the C for being substituted or being unsubstituted6To C60 Aryl or C2To C60Heteroaryl；
L1 is direct key；The C for being substituted or being unsubstituted6To C60Arlydene；Or C2To C60Inferior heteroaryl；
It is selected in the group that Z1 is made of following persons: halogen；-CN；The C for being substituted or being unsubstituted1To C60Alkyl；Be substituted or The C being unsubstituted6To C60Aryl；The C for being substituted or being unsubstituted2To C60Heteroaryl；-SiRR'R"；- P (=O) RR'；And It is unsubstituted or through C1To C20Alkyl, C6To C60Aryl or C2To C60The amido that heteroaryl replaces；
The integer that p is 0 to 4；
The integer that q is 1 to 4；
R6 to R13 is same or different to each other, and selects in the group being made of each independently following persons: hydrogen；Deuterium；Halogen；-CN； The C for being substituted or being unsubstituted1To C60Alkyl；The C for being substituted or being unsubstituted2To C60Alkenyl；It is substituted or is unsubstituted C2To C60Alkynyl；The C for being substituted or being unsubstituted1To C60Alkoxy；The C for being substituted or being unsubstituted3To C60Naphthenic base；Through taking Generation or the C being unsubstituted2To C60Heterocyclylalkyl；The C for being substituted or being unsubstituted6To C60Aryl；It is substituted or is unsubstituted C2To C60Heteroaryl；-SiRR'R"；- P (=O) RR'；And it is unsubstituted or through C1To C20Alkyl, C6To C60Aryl or C2Extremely C60The amido that heteroaryl replaces, or be bonded adjacent to each other, each other to form the aliphatic ring or aromatic hydrocarbon that are substituted or are unsubstituted Two of ring or it is greater than two groups；
M and n is each independently 0 to 5 integer；And
R, R' and R " is same or different to each other, and is each independently hydrogen；Deuterium；-CN；The C for being substituted or being unsubstituted1To C60 Alkyl；The C for being substituted or being unsubstituted3To C60Naphthenic base；The C for being substituted or being unsubstituted6To C60Aryl；Or it is substituted or not The C being substituted2To C60Heteroaryl.
2. heterocyclic compound according to claim 1, wherein at least one of R1 to R5 of chemical formula 1 is by-(L1) p- (Z1) q is indicated, and remaining is hydrogen, and
L1, Z1, p and q have and definition identical in claim 1.
3. heterocyclic compound according to claim 1, wherein R3 of the R1 of chemical formula 1 into R5 is by-(L1) p- (Z1) q table Show, and remaining is hydrogen, and
L1, Z1, p and q have and definition identical in claim 1.
4. heterocyclic compound according to claim 1, wherein R1, R2, R4, R5 and R6 to R13 of chemical formula 1 be respectively It independently is hydrogen or deuterium.
5. heterocyclic compound according to claim 1, wherein R4 of the R1 of chemical formula 1 into R5 is by-(L1) p- (Z1) q table Show, and remaining is hydrogen, and
L1, Z1, p and q have and definition identical in claim 1.
6. heterocyclic compound according to claim 1, wherein R1, R2, R3, R5 and R6 to R13 of chemical formula 1 be respectively It independently is hydrogen or deuterium.
7. heterocyclic compound according to claim 1, wherein chemical formula 1 is indicated by any one of following compound:
8. a kind of organic light emitting apparatus, comprising:
Anode；
Cathode；And
One or more organic material layers being set between the anode and the cathode,
Wherein one or more layers in the organic material layer include the heterocyclic compound as described in any one of claims 1 to 7 Object.
9. organic light emitting apparatus according to claim 8, wherein the organic material layer includes hole blocking layer, electronics note Enter at least one of layer and electronics transfer layer, and the hole blocking layer, the electron injecting layer and the electronics turn Moving at least one of layer includes the heterocyclic compound.
10. organic light emitting apparatus according to claim 8, wherein the organic material layer includes luminescent layer, and the hair Photosphere includes the heterocyclic compound.
11. organic light emitting apparatus according to claim 8, wherein the organic material layer includes hole injection layer, hole Transfer layer and one or more of hole injection and hole transport layer are carried out simultaneously, and it is described in above-mentioned layer to be that one includes Heterocyclic compound.
12. organic light emitting apparatus according to claim 8, wherein the organic material layer includes charge generation layer, and institute Stating charge generation layer includes the heterocyclic compound.
13. the organic light emitting apparatus according to claim 8, comprising:
Anode；
First lamination is set on the anode and including the first luminescent layer；
Charge generation layer is set on first lamination；
Second lamination is set on the charge generation layer and including the second luminescent layer；And
Cathode is set on second lamination.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114341143A (en) * 2019-08-23 2022-04-12 Lt素材株式会社 Heterocyclic compound and organic light-emitting element using same

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102298231B1 (en) * 2017-10-19 2021-09-07 엘티소재주식회사 Hetero-cyclic compound and organic light emitting device using the same
WO2020067595A1 (en) * 2018-09-28 2020-04-02 희성소재(주) Heterocyclic compound and organic light emitting diode comprising same

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020016460A1 (en) * 1999-10-06 2002-02-07 Snow Roger John Heterocyclic compounds useful as inhibitors of tyrosine kinases
CN102010410A (en) * 2009-09-04 2011-04-13 三星移动显示器株式会社 Heterocyclic compound and organic light emitting device including same
CN102763010A (en) * 2009-12-15 2012-10-31 Lg化学株式会社 Polarizing plate, method for producing same and image display device comprising same
WO2015171627A1 (en) * 2014-05-08 2015-11-12 Universal Display Corporation Stabilized imidazophenanthridine materials
WO2016003171A1 (en) * 2014-06-30 2016-01-07 희성소재(주) Heterocyclic compound and organic light emitting element using same
CN105358533A (en) * 2013-12-27 2016-02-24 喜星素材株式会社 Heterocyclic compound and organic light emitting device using same
WO2016137068A1 (en) * 2015-02-24 2016-09-01 주식회사 엘지화학 Hetero ring compound and organic luminescent element comprising same

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101182438B1 (en) * 2009-08-14 2012-09-12 삼성디스플레이 주식회사 Organic light emitting device
KR101579289B1 (en) * 2014-06-30 2015-12-22 희성소재 (주) Hetero-cyclic compound and organic light emitting device using the same

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020016460A1 (en) * 1999-10-06 2002-02-07 Snow Roger John Heterocyclic compounds useful as inhibitors of tyrosine kinases
CN102010410A (en) * 2009-09-04 2011-04-13 三星移动显示器株式会社 Heterocyclic compound and organic light emitting device including same
CN102763010A (en) * 2009-12-15 2012-10-31 Lg化学株式会社 Polarizing plate, method for producing same and image display device comprising same
CN105358533A (en) * 2013-12-27 2016-02-24 喜星素材株式会社 Heterocyclic compound and organic light emitting device using same
WO2015171627A1 (en) * 2014-05-08 2015-11-12 Universal Display Corporation Stabilized imidazophenanthridine materials
WO2016003171A1 (en) * 2014-06-30 2016-01-07 희성소재(주) Heterocyclic compound and organic light emitting element using same
WO2016137068A1 (en) * 2015-02-24 2016-09-01 주식회사 엘지화학 Hetero ring compound and organic luminescent element comprising same

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114341143A (en) * 2019-08-23 2022-04-12 Lt素材株式会社 Heterocyclic compound and organic light-emitting element using same

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